TY - JOUR AU - Béres, Kende Attila AU - Dürvanger, Zsolt AU - Homonnay, Zoltán AU - Nagyné Bereczki, Laura AU - Barta Holló, Berta AU - Farkas, Attila AU - Petruševski, Vladimir M. AU - Kótai, László TI - Insight into the Structure and Redox Chemistry of [Carbonatotetraamminecobalt(III)] Permanganate and Its Monohydrate as Co-Mn-Oxide Catalyst Precursors of the Fischer-Tropsch Synthesis JF - INORGANICS J2 - INORGANICS VL - 12 PY - 2024 IS - 4 SP - 94 SN - 2304-6740 DO - 10.3390/inorganics12040094 UR - https://m2.mtmt.hu/api/publication/34753165 ID - 34753165 AB - [Carbonatotetraamminecobalt(III)] permanganate monohydrate was synthesized first in the metathesis reaction of [Co(NH3)4CO3]NO3 and NaMnO4 in aqueous solution. Its thermal dehydration at 100 °C resulted in phase-pure [Co(NH3)4CO3]MnO4 (compound 1). Compounds 1 and 2 (i.e., the hydrated form) were studied with IR, far-IR, and low-temperature Raman spectroscopies, and their vibrational modes were assigned. The lattice parameters were determined by powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SXRD) methods for the triclinic and orthorhombic compounds 1 and 2, respectively. The detailed structure of compound 2 was determined, and the role of hydrogen bonds in the structural motifs was clarified. UV studies on compounds 1 and 2 showed the distortion of the octahedral geometry of the complex cation during dehydration because of the partial loss of the hydrogen bonds between the crystal water and the ligands of the complex cation. The thermal decomposition consists of a solid phase quasi-intramolecular redox reaction between the ammonia ligands and permanganate anions with the formation of ammonia oxidation products (H2O, NO, N2O, and CO2). The solid phase reaction product is amorphous cobalt manganese oxide containing ammonium, carbonate (and nitrate) anions. The temperature-controlled thermal decomposition of compound 2 in toluene at 110 °C showed that one of the decomposition intermediates is ammonium nitrate. The decomposition intermediates are transformed into Co1.5Mn1.5O4 spinel with MnCo2O4 structure upon further heating. Solid compound 2 gave the spinel at 500 °C both in an inert and air atmosphere, whereas the sample pre-treated in toluene at 110 °C without and with the removal of ammonium nitrate by aqueous washing, gave the spinel already at 300 and 400 °C, respectively. The molten NH4NO3 is a medium to start spinel crystallization, but its decomposition stops further crystal growth of the spinel phase. By this procedure, the particle size of the spinel product as low as ~4.0 nm could be achieved for the treatments at 300 and 400 °C, and it increased only to 5.7 nm at 500 °C. The nano-sized mixed cobalt manganese oxides are potential candidates as Fischer-Tropsch catalysts. LA - English DB - MTMT ER - TY - JOUR AU - May, Nóra Veronika AU - Gál, Gyula Tamás AU - Holczbauer, Tamás AU - Nagyné Bereczki, Laura AU - Di Marco, Valerio B. AU - Bombicz, Petra TI - Gradual Changes in the Aromaticity in a Series of Hydroxypyridine-Carboxylic Acid Derivatives and Their Effect on Tautomerism and Crystal Packing JF - CRYSTAL GROWTH & DESIGN J2 - CRYST GROWTH DES VL - 24 PY - 2024 IS - 3 SP - 1096 EP - 1109 PG - 14 SN - 1528-7483 DO - 10.1021/acs.cgd.3c01118 UR - https://m2.mtmt.hu/api/publication/34616122 ID - 34616122 AB - The keto-enol tautomerism of hydroxypyridine-carboxylic acid (HPC) derivatives with proton transfer between the hydroxyl or carboxyl oxygen atoms was investigated in the case of three 3-hydroxy-4-pyridine-carboxylic acid (3HPC) and eight 4-hydroxy-3-pyridine-carboxylic acid (4HPC) derivatives containing altered pyridine ring substituents. Due to the vicinal position of hydroxyl and carboxylate groups, the hydroxyl proton is involved in an intramolecular H-bond and can very easily transform into the keto or enol tautomer. The proton position was found to correlate with the aromaticity of the pyridine ring, which was described by the Bird index, calculated on the basis of the measured atomic distances. Due to the planar shape of the molecules, pi & sdot;& sdot;& sdot;pi stacking and/or C-O & sdot;& sdot;& sdot;pi interactions were found in all investigated compounds. The molecular properties along with their main supramolecular interactions were compared. Packing arrangements and the main hydrogen-bonding schemes were further compared by using Hirshfeld surface analysis. In the case of the four N-methyl-substituted 4HPC derivatives, the synthon consisting of hydrogen bonds was preserved in the plane of the molecules despite the presence of the various ring substituents. Pairing the 3HPC and 4HPC derivatives, the corresponding compounds exhibited the same molecular shape but different nitrogen positions in the pyridine ring. This gave us the opportunity to examine how the difference in the electron distribution affects only and exclusively the secondary interactions and the arrangement of the molecules in the crystals. The electrostatic potential was calculated and mapped over the Hirshfeld surface, and the calculations of pairwise interaction energies and total energy frameworks were performed using the B3LYP/6-31G-(d,p) energy model. LA - English DB - MTMT ER - TY - JOUR AU - Barta Holló, Berta AU - Bayat, Niloofar AU - Nagyné Bereczki, Laura AU - Petrusevski, Vladimir AU - Béres, Kende Attila AU - Farkas, Attila AU - Szilágyi, Imre Miklós AU - Kótai, László TI - Spectroscopic and structural characterization of hexaamminecobalt(III) dibromide permanganate JF - JOURNAL OF THE SERBIAN CHEMICAL SOCIETY J2 - J SERB CHEM SOC VL - 88 PY - 2023 IS - 12 SP - 1237 EP - 1252 PG - 16 SN - 0352-5139 DO - 10.2298/JSC230702062B UR - https://m2.mtmt.hu/api/publication/34316828 ID - 34316828 N1 - Export Date: 23 February 2024 CODEN: JSCSE Correspondence Address: Kótai, L.; Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2., Hungary; email: kotai.laszlo@ttk.hu AB - Structural and spectroscopic characterization (SXRD, IR, liq. N2 temperature Raman, UV) of hexaamminecobalt(III) dibromide permanganate, [Co(NH3)6]Br2(MnO4) (compound 1) are described. There is a 3D hydrogen bond network including N-H???O-Mn and N-H???Br interactions, which could serve as potential reaction centers for solid-phase redox reactions between the ammonia ligands and/or bromide ions as reductants and permanganate ions as oxidant agents. The effect of the nature of halogen ions on the structural and spectroscopic properties of [Co(NH3)6]Br2(MnO4) and the analogous chloride compound, [Co(NH3)6]Cl2(MnO4) (compound 2) are discussed in detail. LA - English DB - MTMT ER - TY - JOUR AU - Martiz Chalen, Jose Alejandro AU - Károly, Zoltán AU - Nagyné Bereczki, Laura AU - Trif, László AU - Farkas, Attila AU - Kállay-Menyhárd, Alfréd AU - Kótai, László TI - Carbonization of Zr-loaded thiourea-functionalized styrene-divinylbenzene copolymers: An easy was to synthesize Nano-ZrO2@C and Nano-(ZrC, ZrO2)@C composites JF - JOURNAL OF COMPOSITES SCIENCE J2 - J COMPOSITES SCI VL - 7 PY - 2023 PG - 15 SN - 2504-477X DO - 10.3390/jcs7080306 UR - https://m2.mtmt.hu/api/publication/34077482 ID - 34077482 N1 - Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, Budapest, H-1117, Hungary Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, Műegyetem rakpart 3, Budapest, H-1111, Hungary Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Műegyetem rakpart 3, Budapest, H-1111, Hungary Deuton-X Ltd, Selmeci u. 89, Érd, H-2030, Hungary Export Date: 4 September 2023 Correspondence Address: Kótai, L.; Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, Hungary; email: kotai.laszlo@ttk.hu LA - English DB - MTMT ER - TY - JOUR AU - Béres, Kende Attila AU - Homonnay, Zoltán AU - Nagyné Bereczki, Laura AU - Dürvanger, Zsolt AU - Petruševski, Vladimir M. AU - Farkas, Attila AU - Kótai, László TI - Crystal Nanoarchitectonics and Characterization of the Octahedral Iron(III)–Nitrate Complexes with Isomer Dimethylurea Ligands JF - CRYSTALS J2 - CRYSTALS VL - 13 PY - 2023 IS - 7 PG - 20 SN - 2073-4352 DO - 10.3390/cryst13071019 UR - https://m2.mtmt.hu/api/publication/34037505 ID - 34037505 N1 - Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Budapest, H-1117, Hungary György Hevesy PhD School of Chemistry, ELTE Eötvös Loránd University, Budapest, H-1117, Hungary Institute of Chemistry, ELTE Eötvös Loránd University, Budapest, H-1117, Hungary Centre for Structural Science, Research Centre for Natural Sciences, Budapest, H-1117, Hungary ELKH-ELTE Protein Modelling Research Group, Budapest, H-1117, Hungary Structural Chemistry and Biology Laboratory, Institute of Chemistry, ELTE Eötvös Loránd University, Budapest, H-1117, Hungary Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, Skopje, MK-1000, North Macedonia Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Budapest, H-1111, Hungary Deuton-X Ltd, Érd, H-2030, Hungary Export Date: 14 August 2023 Correspondence Address: Kótai, L.; Institute of Materials and Environmental Chemistry, Hungary; email: kotai.laszlo@ttk.hu AB - Three octahedral iron(III) nitrate complexes with dimethylated urea ligand isomers, [hexakis(N,N’-dimethylurea-O)iron(III)] nitrate (compound 1), trans-[diaquatetrakis(N,N-dimethylurea-O)iron(III)] nitrate (compound 2), and [hexakis(N,N-dimethylurea-O)iron(III)] nitrate trihydrate (compound 3) were prepared and characterized with single crystal X-ray diffraction, IR, Raman and UV–Vis methods. In compounds 1 and 3, six dimethylurea ligands coordinate to the central FeIII ion via the oxygen in octahedral geometry and the ligands are arranged in a propeller-like manner, dividing the complex cations into two sides. In compound 1, the dimethylurea propellers screw in the opposite direction on the two sides of the complex and in compound 3, they are arranged with the same handedness on the two sides. The complexes have helical chirality. The two sides of the complex cations differ not only in the rotation direction of the ligands but also in the hydrogen bond formation. On one side of the complex cation, the ligands form intermolecular hydrogen bonds only with the crystal waters, meanwhile on the other side of the complex, the ligands form hydrogen bonds only with the nitrate ions. In compound 2, [Fe(N,N-dimethylurea)4(H2O)2]3+ cations form layers that are separated by interconnected NO3− ions forming a hydrogen bonding system and connecting the complex cations A-s and B-s. The three crystallographically different nitrate ions each form four hydrogen bonds in a way that they have one bidentate O atom and two monodentate O atoms; however, the anions differ in their hydrogen bonding. The spectroscopic characteristics of compound 2 were determined by IR measurements on the deuterated compound 2 as well. LA - English DB - MTMT ER - TY - JOUR AU - Bosits, Miklós Hunor AU - Nagyné Bereczki, Laura AU - Bombicz, Petra AU - Szalay, Zsofia AU - Pataki, Hajnalka AU - Demeter, Adam TI - Design of diastereomeric salt resolution via multicomponent system characterization: a case study with hydrate formation JF - CRYSTENGCOMM J2 - CRYSTENGCOMM VL - 25 PY - 2023 IS - 4 SP - 641 EP - 652 PG - 12 SN - 1466-8033 DO - 10.1039/d2ce01490d UR - https://m2.mtmt.hu/api/publication/33760642 ID - 33760642 N1 - Funding Agency and Grant Number: Ministry of Innovation and Technology of Hungary from the National Research, Development and Innovation Fund [FK-143019, K-124544]; Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences Funding text: This work has been implemented with the support provided by the Ministry of Innovation and Technology of Hungary from the National Research, Development and Innovation Fund, financed under the [FK-143019 and K-124544] funding scheme. H. P. is thankful for the Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences. The authors greatly acknowledge the continuous support of colleagues from the Polymorphism Research Team at Gedeon Richter Plc., who contributed to this work with numerous daily technical help. AB - Diastereomeric salt crystallization is a convenient method to resolve chiral drug substances when other separation methods like preferential crystallization and solid-state deracemization cannot be applied directly. This is the case of the antiepileptic pregabalin, which is a racemate-forming compound with recently discovered hydrate-forming activity. In this study, the quaternary system of pregabalin enantiomers, l-tartaric acid and water was investigated by the characterization of relevant solid forms and the measurement of solubilities and solid-liquid equilibria. This information was used to outline phase diagrams in the specific quaternary space and create a thermodynamic model based on solubility product constants to simulate the effect of variable parameters on the resolution process. Thus, a set of optimal temperature pairs were identified with similar selectivity along the so-called purity line in the region of 10-40 degrees C. This line was adjusted experimentally, and a realistic correction of 3 degrees C was made. Our method provided a quick process with low material requirements to design diastereomeric salt resolution. Finally, a proof of concept resolution experiment was conducted, where a diastereomerically pure product was obtained with 51.6% yield and 153 mg (g water)(-1) productivity. Design of a chiral resolution process with thermodynamic control. LA - English DB - MTMT ER - TY - JOUR AU - Béres, Kende Attila AU - Szilágyi, Fanni AU - Homonnay, Zoltán AU - Dürvanger, Zsolt AU - Nagyné Bereczki, Laura AU - Trif, László AU - Petruševski, Vladimir M. AU - Farkas, Attila AU - Bayat, Niloofar AU - Kótai, László TI - Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions JF - INORGANICS J2 - INORGANICS VL - 11 PY - 2023 IS - 2 PG - 21 SN - 2304-6740 DO - 10.3390/inorganics11020068 UR - https://m2.mtmt.hu/api/publication/33610854 ID - 33610854 N1 - Correspondence Address: Béres, K.A.; Research Centre for Natural Sciences, Magyar Tudósok krt. 2, Hungary; email: beres.kende.attila@ttk.hu Correspondence Address: Kótai, L.; Research Centre for Natural Sciences, Magyar Tudósok krt. 2, Hungary; email: kotai.laszlo@ttk.hu AB - [κ2-O,O′-Carbonatotetraamminecobalt(III)] iodide, or [Co(NH3)4CO3]I, named in this paper as compound 1, was prepared and characterized comprehensively with spectroscopic (IR, Raman and UV) and single-crystal X-ray diffraction methods. Compound 1 was orthorhombic, and isomorphous with the analogous bromide. The four ammonia ligands and the carbonate anion were coordinated to the central cobalt cation in a distorted octahedral geometry. The carbonate ion formed a four-membered symmetric planar chelate ring. The complex cations were bound to each other by N-H···O hydrogen bonds and formed zigzag sheets via an extended 2D hydrogen bond network. The complex cations and iodide ions were arranged into ion pairs and each cation bound its iodide pair through three hydrogen bonds. The thermal decomposition started with the oxidation of the iodide ion by CoIII in the solid phase resulting in [Co(NH3)4CO3] and I2. This intermediate CoII-complex in situ decomposed into Co3O4 and C-N bond containing intermediates. In inert atmosphere, CO or C-N bond containing compounds, and also, due to the in situ decomposition of CoCO3 intermediate, Co3O4 was formed. The quasi-intramolecular solid-phase redox reaction of [Co(NH3)4CO3] might have resulted in the formation of C-N bond containing compounds with substoichiometric release of ammonia and CO2 from compound 1. The C-N bond containing intermediates reduced Co3O4 into CoO and Co, whereas in oxygen-containing atmosphere, the end-product was Co3O4, even at 200 °C, and the endothermic ligand loss reaction coincided with the consecutive exothermic oxidation processes. LA - English DB - MTMT ER - TY - JOUR AU - Kótai, László AU - Petruševski, Vladimir M. AU - Nagyné Bereczki, Laura AU - Béres, Kende Attila TI - Catalytic Properties of the Spinel-Like CuxMn3−xO4 Copper Manganese Oxides—An Overview JF - CATALYSTS J2 - CATALYSTS VL - 13 PY - 2023 IS - 1 PG - 31 SN - 2073-4344 DO - 10.3390/catal13010129 UR - https://m2.mtmt.hu/api/publication/33550015 ID - 33550015 AB - Copper manganese oxide spinels and related (multiphase) materials with the formula CuxMn3−xO4 are the active catalysts in a wide variety of industrially important processes due to their great diversity in their phase relations, metal ion valence/site distribution, and chemical properties. In this review, we summarize the preparation methods and their effects on the composition, properties, and catalytic properties of various CuxMn3−xO4 catalysts with various Cu/Mn ratios. The main summarized catalytic reactions are the oxidation of carbon monoxide, nitrogen oxide, and hydrogen sulfide and the oxidative removal of organic solvents such as benzene, toluene, and xylene from the air. Some industrially important reactions (steam reforming of methanol or synthesis gas) and the manufacture of organic chemicals (methyl formate, propylene oxide, and benzyl alcohol) catalyzed by CuxMn3−xO4 spinels are also reviewed. LA - English DB - MTMT ER - TY - JOUR AU - Petrasheuskaya, Tatsiana AU - Kovács, Ferenc AU - Igaz, Nóra AU - Rónavári, Andrea AU - Hajdu, Bálint AU - Nagyné Bereczki, Laura AU - May, Nóra Veronika AU - Spengler, Gabriella AU - Gyurcsik, Béla AU - Csontné Kiricsi, Mónika AU - Nagyné Frank, Éva AU - Enyedy, Éva Anna TI - Estradiol-Based Salicylaldehyde (Thio)semicarbazones and Their Copper Complexes with Anticancer, Antibacterial and Antioxidant Activities JF - MOLECULES J2 - MOLECULES VL - 28 PY - 2023 IS - 1 PG - 26 SN - 1420-3049 DO - 10.3390/molecules28010054 UR - https://m2.mtmt.hu/api/publication/33416616 ID - 33416616 N1 - Funding Agency and Grant Number: National Research, Development and Innovation Office-NKFIA (Hungary) [TKP-2021-EGA-32]; OTKA [K124544]; 'Lendulet' Programme ELKH [LP2019-6/2019]; Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences [BO/00158/22/5]; New National Excellence Program of the Ministry for Culture and Innovation from the source of the National Research, Development and Innovation Fund [UNKP-22-5-SZTE-588] Funding text: This work was supported by the National Research, Development and Innovation Office-NKFIA (Hungary) through project TKP-2021-EGA-32 and OTKA grant K124544. The support of the 'Lendulet' Programme (ELKH, LP2019-6/2019) is also acknowledged. G.S. was supported by the Janos Bolyai Research Scholarship (BO/00158/22/5) of the Hungarian Academy of Sciences and by the UNKP-22-5-SZTE-588 New National Excellence Program of the Ministry for Culture and Innovation from the source of the National Research, Development and Innovation Fund. AB - A series of novel estradiol-based salicylaldehyde (thio)semicarbazones ((T)SCs) bearing (O,N,S) and (O,N,O) donor sets and their Cu(II) complexes were developed and characterized in detail by 1H and ¹³C nuclear magnetic resonance spectroscopy, UV–visible and electron paramagnetic resonance spectroscopy, electrospray ionization mass spectrometry and elemental analysis. The structure of the Cu(II)-estradiol-semicarbazone complex was revealed by X-ray crystallography. Proton dissociation constants of the ligands and stability constants of the metal complexes were determined in 30% (v/v) DMSO/H2O. Estradiol-(T)SCs form mono-ligand complexes with Cu(II) ions and exhibit high stability with the exception of estradiol-SC. The Cu(II) complexes of estradiol-TSC and its N,N-dimethyl derivative displayed the highest cytotoxicity among the tested compounds in MCF-7, MCF-7 KCR, DU-145, and A549 cancer cells. The complexes do not damage DNA according to both in vitro cell-free and cellular assays. All the Cu(II)-TSC complexes revealed significant activity against the Gram-positive Staphylococcus aureus bacteria strain. Estradiol-TSCs showed efficient antioxidant activity, which was decreased by complexation with Cu(II) ions. The exchange of estrone moiety to estradiol did not result in significant changes to physico-chemical and biological properties. LA - English DB - MTMT ER - TY - JOUR AU - Bîtcan, Ioan AU - Petrovici, Andreea AU - Pellis, Alessandro AU - Klébert, Szilvia AU - Károly, Zoltán AU - Nagyné Bereczki, Laura AU - Péter, Francisc AU - Todea, Anamaria TI - Enzymatic route for selective glycerol oxidation using covalently immobilized laccases JF - ENZYME AND MICROBIAL TECHNOLOGY J2 - ENZYME MICROB TECH VL - 163 PY - 2023 PG - 14 SN - 0141-0229 DO - 10.1016/j.enzmictec.2022.110168 UR - https://m2.mtmt.hu/api/publication/33290419 ID - 33290419 AB - Glycerol is an important starting material for the synthesis of many chemical compounds and its selective oxidation represents an efficient way to produce value-added compounds. Glyceric acid, one of these selective oxidation products, is an important intermediate in the food, medicine, cosmetics, and light industries. In this work, four commercially available native laccases were screened for glycerol oxidation using different initiators, and the two most efficient biocatalysts were covalently immobilized on functionalized magnetic and polymethacrylate (LifetechTM) solid supports. Apart from the mostly employed Fe3O4 magnetic particles, in this work Ni-Zn or Ni-Zn-Co spinel ferrite (MFe2O4) microparticles were used. Particularly, the utilization (for the first time for laccase immobilization) of Ni-Zn ferrite support Ni0.7Zn0.3Fe2O4 functionalized with 3-aminopropyl-trimethoxysilane, via crosslinking by glutaraldehyde and reduction with NaBH4 led to excellent biocatalytic efficiency and stability. These results confirm the feasibility of Trametes versicolor laccase for covalent bonding, as presumed by computational modelling. The resulted enzymatic preparations were characterized in detail in terms of stability and reusability, demonstrating enhanced storage, pH and thermal stability compared to the native enzymes. The most active biocatalysts (790.93 [U/g]) were successfully used for glycerol oxidation and the specific conversion in glyceric acid exceeded 50%. LA - English DB - MTMT ER -